Instytut Podstawowych Problemów Techniki

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Atopic dermatitis (AD) is a chronic inflammatory skin disease with a complex etiology that lacks effective treatment. The therapeutic goals include alleviating symptoms, such as moisturizing and applying antibacterial and anti-inflammatory medications. Hence, there is an urgent need to develop a patch that effectively alleviates most of the AD symptoms. In this study, we employed a “green” cross-linking approach of poly(vinyl alcohol) (PVA) using glycerol, and we combined it with polyacrylonitrile (PAN) to fabricate core–shell (CS) nanofibers through electrospinning. Our designed structure offers multiple benefits as the core ensures controlled drug release and increases the strength of the patch, while the shell provides skin moisturization and exudate absorption. The efficient PVA cross-linking method facilitates the inclusion of sensitive molecules such as fermented oils. In vitro studies demonstrate the patches’ exceptional biocompatibility and efficacy in minimizing cell ingrowth into the CS structure containing argan oil, a property highly desirable for easy removal of the patch. Histological examinations conducted on an ex vivo model showed the nonirritant properties of developed patches. Furthermore, the eradication of Staphylococcus aureus bacteria confirms the potential use of CS nanofibers loaded with argan oil or norfloxacin, separately, as an antibacterial patch for infected AD wounds. In vivo patch application studies on patients, including one with AD, demonstrated ideal patches’ moisturizing effect. This innovative approach shows significant promise in enhancing life quality for AD sufferers by improving skin hydration and avoiding infections.

Słowa kluczowe:

atopic dermatitis, core−shell electrospun nanofibers, antibacterial, mucoadhesive, moisturizing patch

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A new generation of an FFP2 (Filtering Face Piece of type 2) smart face mask is achieved by integrating broadband hybrid nanomaterials and a self-assembled optical metasurface. The multifunctional FFP2 face mask shows simultaneously white light-assisted on-demand disinfection properties and versatile biosensing capabilities. These properties are achieved by a powerful combination of white light thermoplasmonic responsive hybrid nanomaterials, which provide excellent photo-thermal disinfection properties, and optical metasurface-based colorimetric biosensors, with a very low limit of pathogens detection. The realized system is studied in optical, morphological, spectroscopic, and cell viability assay experiments and environmental monitoring of harmful pathogens, thus highlighting the extraordinary properties in reusability and pathogens detection of the innovative face mask.

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Intervertebral disc (IVD) degeneration is a leading cause of lower back pain (LBP). Current treatments primarily address symptoms without halting the degenerative process. Cell transplantation offers a promising approach for early-stage IVD degeneration, but challenges such as cell viability, retention, and harsh host environments limit its efficacy. This study aimed to compare the injectability and biocompatibility of human nucleus pulposus cells (hNPC) attached to two types of microscaffolds designed for minimally invasive delivery to IVD. Microscaffolds are developed from poly(lactic-co-glycolic acid) (PLGA) using electrospinning and femtosecond laser structuration. These microscaffolds are tested for their physical properties, injectability, and biocompatibility. This study evaluates cell adhesion, proliferation, and survival in vitro and ex vivo within a hydrogel-based nucleus pulposus model. The microscaffolds demonstrate enhanced surface architecture, facilitating cell adhesion and proliferation. Laser structuration improved porosity, supporting cell attachment and extracellular matrix deposition. Injectability tests show that microscaffolds can be delivered through small-gauge needles with minimal force, maintaining high cell viability. The findings suggest that laser-structured PLGA microscaffolds are viable for minimally invasive cell delivery. These microscaffolds enhance cell viability and retention, offering potential improvements in the therapeutic efficiency of cell-based treatments for discogenic LBP.

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Bone defects resulting from congenital anomalies and trauma pose significant clinical challenges for orthopedics surgeries, where bone tissue engineering (BTE) aims to address these challenges by repairing defects that fail to heal spontaneously. Despite numerous advances, BTE still faces several challenges, i.e., difficulties in detecting and tracking implanted cells, high costs, and regulatory approval hurdles. Biomaterials promise to revolutionize bone grafting procedures, heralding a new era of regenerative medicine and advancing patient outcomes worldwide. Specifically, novel bioactive biomaterials have been developed that promote cell adhesion, proliferation, and differentiation and have osteoconductive and osteoinductive characteristics, stimulating tissue regeneration and repair, particularly in complex skeletal defects caused by trauma, degeneration, and neoplasia. A wide array of biological therapeutics for bone regeneration have emerged, drawing from the diverse spectrum of gene therapy, immune cell interactions, and RNA molecules. This review will provide insights into the current state and potential of future strategies for bone regeneration.

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Detection of lysozyme levels in ocular fluids is considered crucial for diagnosing and monitoring various health and eye conditions, including dry-eye syndrome. Hydrogel-based nanocomposites have been demonstrated to be one of the most promising platforms for fast and accurate sensing of different biomolecules. In this work, hydrogel, electrospun nanofibers, and plasmonic nanoparticles are combined to fabricate a sensitive and easy-to-use biosensor for lysozyme. Poly(L-lactide-co-caprolactone) (PLCL) nanofibers were covered with silver nanoplates (AgNPls), providing a stable plasmonic platform, where a poly(N-isopropylacrylamide)-based (PNIPAAm) hydrogel layer allows mobility and good integration of the biomolecules. By integrating these components, the platform can also exhibit a colorimetric response to the concentration of lysozyme, allowing for easy and non-invasive monitoring. Quantitative biosensing operates on the principle of localized surface plasmon resonance (LSPR) induced by plasmonic nanoparticles. Chemical, structural, thermal, and optical characterizations were performed on each platform layer, and the platform's ability to detect lysozyme at concentrations relevant to those found in tears of patients with dry-eye syndrome and other related diseases was investigated by colorimetry and UV-Vis spectroscopy. This biosensor's sensitivity and rapid response time, alongside the easy detection by the naked eye, make it a promising tool for early diagnosis and treatment monitoring of eye diseases.

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Bacterial keratitis (BK) is a severe eye infection commonly associated with Staphylococcus aureus (S. aureus), posing a significant risk to vision, especially among contact lens wearers. This research introduces a novel smart nanoplatform (deMS@cNF), developed from demineralized mussel shells (deMS) and reinforced with chitin (CT) nanofibrils, specifically designed for portable photothermal disinfection of contact lenses. The nanoplatform leverages the photothermal properties of eumelanin in mussel shells (MS), which, when activated by a simple bike flashlight, rapidly heats to temperatures up to 95 °C, effectively destroying bacterial contamination. In vitro tests demonstrate that the nanoplatform is biocompatible and non-toxic, making it suitable for medical applications. This study highlights an innovative approach to converting marine biowaste into a safe, effective, and low-cost portable method for disinfecting contact lenses, showcasing the potential of the deMS@cNF platform for broader antimicrobial applications.

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Hydrogels with multifunctional properties activated at specific times have gained significant attention in the biomedical field. As bacterial infections can cause severe complications that negatively impact wound repair, herein, we present the development of a stimuli-responsive, injectable, and in situ-forming hydrogel with antibacterial, self-healing, and drug-delivery properties. In this study, we prepared a Pluronic F-127 (PF127) and sodium alginate (SA)-based hydrogel that can be targeted to a specific tissue via injection. The PF127/SA hydrogel was incorporated with polymeric short-filaments (SFs) containing an anti-inflammatory drug – ketoprofen, and stimuli-responsive polydopamine (PDA) particles. The hydrogel, after injection, could be in situ gelated at the body temperature, showing great in vitro stability and self-healing ability after 4 h of incubation. The SFs and PDA improved the hydrogel injectability and compressive strength. The introduction of PDA significantly accelerated the KET release under near-infrared light exposure and extended its release validity period. The excellent composites’ photo-thermal performance led to antibacterial activity against representative Gram-positive and Gram-negative bacteria, resulting in 99.9% E. coli and S. aureus eradication after 10 min of NIR light irradiation. In vitro, fibroblast L929 cell studies confirmed the materials’ biocompatibility and paved the way toward further in vivo and clinical application of the system for chronic wound treatments.

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The shortage of face masks and the lack of antipathogenic functions has been significant since the recent pandemic's inception. Moreover, the disposal of an enormous number of contaminated face masks not only carries a significant environmental impact but also escalates the risk of cross-contamination. This study proposes a strategy to upgrade available surgical masks into antibacterial masks with enhanced particle and bacterial filtration. Plasmonic nanoparticles can provide photodynamic and photothermal functionalities for surgical masks. For this purpose, gold nanorods act as on-demand agents to eliminate pathogens on the surface of the masks upon near-infrared light irradiation. Additionally, the modified masks are furnished with polymer electrospun nanofibrous layers. These electrospun layers can enhance the particle and bacterial filtration efficiency, not at the cost of the pressure drop of the mask. Consequently, fabricating these prototype masks could be a practical approach to upgrading the available masks to alleviate the environmental toll of disposable face masks.

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Hierarchical nanostructures fabricate by electrospinning in combination with light-responsive agents offer promising scenarios for developing novel activable antibacterial interfaces. This study introduces an innovative antibacterial face mask developed from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers integrated with indocyanine green (ICG), targeting the urgent need for effective antimicrobial protection for community health workers. The research focuses on fabricating and characterizing this nanofibrous material, evaluating the mask's mechanical and chemical properties, investigating its particle filtration, and assessing antibacterial efficacy under photothermal conditions for reactive oxygen species (ROS) generation. The PHBV/ICG nanofibers are produced using an electrospinning process, and the nanofibrous construct's morphology, structure, and photothermal response are investigated. The antibacterial efficacy of the nanofibers is tested, and substantial bacterial inactivation under both near-infrared (NIR) and solar irradiation is demonstrated due to the photothermal response of the nanofibers. The material's photothermal response is further analyzed under cyclic irradiation to simulate real-world conditions, confirming its durability and consistency. This study highlights the synergistic impact of PHBV and ICG in enhancing antibacterial activity, presenting a biocompatible and environmentally friendly solution. These findings offer a promising path for developing innovative face masks that contribute significantly to the field of antibacterial materials and solve critical public health challenges.

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Recently, there has been a surge of interest in developing new types of photothermal materials driven by the ongoing demand for efficient energy conversion, environmental concerns, and the need for sustainable solutions. However, many existing photothermal materials face limitations such as high production costs or narrow absorption bands, hindering their widespread application. In response to these challenges, researchers have redirected their focus toward harnessing the untapped potential of organic waste-derived and bioderived materials. These materials, with photothermal properties derived from their intrinsic composition or transformative processes, offer a sustainable and cost-effective alternative. This review provides an extended categorization of organic waste-derived and bioderived materials based on their origin. Additionally, we investigate the mechanisms underlying the photothermal properties of these materials. Key findings highlight their high photothermal efficiency and versatility in applications such as water and energy harvesting, desalination, biomedical applications, deicing, waste treatment, and environmental remediation. Through their versatile utilization, they demonstrate immense potential in fostering sustainability and support the transition toward a greener and more resilient future. The authors’ perspective on the challenges and potentials of platforms based on these materials is also included, highlighting their immense potential for real-world implementation.

Słowa kluczowe:

photothermal materials, organic waste valorization, bioderived materials

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Functional antibacterial textiles fabricated from a hybrid of organic waste-derived and bio-inspired materials offer sustainable solutions for preventing microbial infections. In this work, we developed a novel antibacterial textile created through the valorization of spent coffee grounds (SCG). Electrospinning and electrospraying techniques were employed to integrate the biowaste within a polymeric nanofiber matrix, ensuring uniform particle distribution and providing structural support for enhanced applicability. Modification with polydopamine (PDA) significantly enhanced the textile's photothermal performance. Specific attention was paid to understanding the relation between temperature change and key variables, including the surrounding liquid volume, textile layer stacking, and applied laser power. Developed platforms demonstrated excellent photothermal stability. While the SCG-based textile demonstrated exceptional biocompatibility, the PDA-modified textile effectively eradicated Staphylococcus aureus (S. aureus) under near-infrared (NIR) irradiation. The developed textiles in our work demonstrate a dynamic balance between biocompatibility and on-demand antibacterial functionality, offering adaptable solutions in accordance with the desired application.

Słowa kluczowe:

Organic waste valorization, Spent coffee grounds, Micro-nanostructured textiles, Bio-inspired photothermal agents, Polydopamine, Antibacterial textiles

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Development and step-by-step characterizations of a novel cationic thiophene based copolymer (P1buP), including ionic phosphonium salt and dye-tetraphenylporphyrin (TPP) moiety in side chains, with an iconic property of solubility in a wide range of polar solvents is reported. Synthesized by using simple, low-cost, and straightforward procedures, the material is used to fabricate completely halogen-free (i.e., from ethanol) ternary organic solar cells (OSCs), in the presence of an alcohol-soluble ionic 3,4-dialkoxythiophene based homopolymer (P2buP) and a serinol-fullerene derivative (C60-Ser). Indeed, thanks to co-sensitization techniques, where multiple dyes harvest different parts of the solar spectrum, the power conversion efficiency of the best final device dramatically increases up to nearly 5.0%, as the light absorption is usually optimized. Additionally, since the use of a cathode interlayer in OSCs also plays a pivotal role in electron extraction and device stability, a possible application of the ionic TPP material as the interfacial layer is also investigated. Furthermore, to improve and optimize the best performing device, a successful post-metalation with Zn of the porphyrin core is carried out, and a ternary OSC (P1buP:P2buP:C60-Ser = 0.33:0.67:1 w/w) is fabricated, resulting in a photoconversion efficiency (PCE) of ∼6.0%.

Słowa kluczowe:

Ionic dye-tetraphenylporphyrin, Co-sensitization, Ternary OSCs, Cathode interlayers, Halogen-free deposition

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Polycaprolactone (PCL), a recognized biopolymer, has emerged as a prominent choice for diverse biomedical endeavors due to its good mechanical properties, exceptional biocompatibility, and tunable properties. These attributes render PCL a suitable alternative biomaterial to use in biofabrication, especially the electrospinning technique, facilitating the production of nanofibers with varied dimensions and functionalities. However, the inherent hydrophobicity of PCL nanofibers can pose limitations. Conversely, acrylamide-based hydrogels, characterized by their interconnected porosity, significant water retention, and responsive behavior, present an ideal matrix for numerous biomedical applications. By merging these two materials, one can harness their collective strengths while potentially mitigating individual limitations. A robust interface and effective anchorage during the composite fabrication are pivotal for the optimal performance of the nanoplatforms. Nanoplatforms are subject to varying degrees of tension and physical alterations depending on their specific applications. This is particularly pertinent in the case of layered nanostructures, which require careful consideration to maintain structural stability and functional integrity in their intended applications. In this study, we delve into the influence of the fiber dimensions, orientation and surface modifications of the nanofibrous layer and the hydrogel layer's crosslinking density on their intralayer interface to determine the optimal approach. Comprehensive mechanical pull-out tests offer insights into the interfacial adhesion and anchorage between the layers. Notably, plasma treatment of the hydrophobic nanofibers and the stiffness of the hydrogel layer significantly enhance the mechanical effort required for fiber extraction from the hydrogels, indicating improved anchorage. Furthermore, biocompatibility assessments confirm the potential biomedical applications of the proposed nanoplatforms.

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In neuroscience, the acquisition of neural signals from the brain cortex is crucial to analyze brain processes, detect neurological disorders, and offer therapeutic brain–computer interfaces. The design of neural interfaces conformable to the brain tissue is one of today’s major challenges since the insufficient biocompatibility of those systems provokes a fibrotic encapsulation response, leading to an inaccurate signal recording and tissue damage precluding long-term/permanent implants. The design and production of a novel soft neural biointerface made of polyacrylamide hydrogels loaded with plasmonic silver nanocubes are reported herein. Hydrogels are surrounded by a silicon-based template as a supporting element for guaranteeing an intimate neural-hydrogel contact while making possible stable recordings from specific sites in the brain cortex. The nanostructured hydrogels show superior electroconductivity while mimicking the mechanical characteristics of the brain tissue. Furthermore, in vitro biological tests performed by culturing neural progenitor cells demonstrate the biocompatibility of hydrogels along with neuronal differentiation. In vivo chronic neuroinflammation tests on a mouse model show no adverse immune response toward the nanostructured hydrogel-based neural interface. Additionally, electrocorticography acquisitions indicate that the proposed platform permits long-term efficient recordings of neural signals, revealing the suitability of the system as a chronic neural biointerface.

Słowa kluczowe:

brain−machine interface,conductive hydrogels,nanostructured biomaterials,in vitro and in vivo biocompatibility,long-term neural recording

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Current treatments of degenerated intervertebral discs often provide only temporary relief or address specific causes, necessitating the exploration of alternative therapies. Cell-based regenerative approaches showed promise in many clinical trials, but
limitations such as cell death during injection and a harsh disk environment hinder their effectiveness. Injectable microscaffolds offer a solution by providing a supportive microenvironment for cell delivery and enhancing bioactivity. This study evaluated the
safety and feasibility of electrospun nanofibrous microscaffolds modified with chitosan (CH) and chondroitin sulfate (CS) for treating degenerated NP tissue in a large animal model. The microscaffolds facilitated cell attachment and acted as an effective delivery system, preventing cell leakage under a high disc pressure. Combining microscaffolds with bone marrow-derived mesenchymal stromal cells demonstrated no cytotoxic effects and proliferation over the entire microscaffolds. The administration of cells attached to microscaffolds into the NP positively influenced the regeneration process of the intervertebral disc. Injectable poly(L-lactide-co-glycolide) and poly(L-lactide) microscaffolds enriched with CH or CS, having a fibrous structure, showed the potential to promote intervertebral disc regeneration. These features collectively address critical challenges in the fields of tissue engineering and regenerative medicine, particularly in the context of intervertebral disc degeneration.

Słowa kluczowe:

microscaffolds,cell carriers,injectable biomaterials,intervertebral disc,laser micromachining,electrospinning

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As scientists discovered that raw neurological signals could translate into bioelectric information, brain–machine interfaces (BMI) for experimental and clinical studies have experienced massive growth. Developing suitable materials for bioelectronic devices to be used for real-time recording and data digitalizing has three important necessitates which should be covered. Biocompatibility, electrical conductivity, and having mechanical properties similar to soft brain tissue to decrease mechanical mismatch should be adopted for all materials. In this review, inorganic nanoparticles and intrinsically conducting polymers are discussed to impart electrical conductivity to systems, where soft materials such as hydrogels can offer reliable mechanical properties and a biocompatible substrate. Interpenetrating hydrogel networks offer more mechanical stability and provide a path for incorporating polymers with desired properties into one strong network. Promising fabrication methods, like electrospinning and additive manufacturing, allow scientists to customize designs for each application and reach the maximum potential for the system. In the near future, it is desired to fabricate biohybrid conducting polymer-based interfaces loaded with cells, giving the opportunity for simultaneous stimulation and regeneration. Developing multi-modal BMIs, Using artificial intelligence and machine learning to design advanced materials are among the future goals for this field.

Słowa kluczowe:

3D printing,brain–machine interface,conductive hydrogels,electrospinning,neural recording

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Recent advances in the field of skin patches have promoted the development of wearable and implantable bioelectronics for long-term, continuous healthcare management and targeted therapy. However, the design of electronic skin (e-skin) patches with stretchable components is still challenging and requires an in-depth understanding of the skin-attachable substrate layer, functional biomaterials and advanced self-powered electronics. In this comprehensive review, we present the evolution of skin patches from functional nanostructured materials to multi-functional and stimuli-responsive patches towards flexible substrates and emerging biomaterials for e-skin patches, including the material selection, structure design and promising applications. Stretchable sensors and self-powered e-skin patches are also discussed, ranging from electrical stimulation for clinical procedures to continuous health monitoring and integrated systems for comprehensive healthcare management. Moreover, an integrated energy harvester with bioelectronics enables the fabrication of self-powered electronic skin patches, which can effectively solve the energy supply and overcome the drawbacks induced by bulky battery-driven devices. However, to realize the full potential offered by these advancements, several challenges must be addressed for next-generation e-skin patches. Finally, future opportunities and positive outlooks are presented on the future directions of bioelectronics. It is believed that innovative material design, structure engineering, and in-depth study of fundamental principles can foster the rapid evolution of electronic skin patches, and eventually enable self-powered close-looped bioelectronic systems to benefit mankind.

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In this study, we introduce a novel family of symmetrical thiophene-based small molecules with a Donor–Acceptor–Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4-b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole-thiophene derivative. Using Density Functional Theory (DFT), we investigate how the molecular geometry and strength of the central acceptor unit impact the redox and spectroscopic properties. Notably, the incorporation of Pz and Tz moieties induces a significant redshift in the absorption and emission spectra, which extend into the near-infrared (NIR) region, simultaneously reducing their energy gaps (~1.4-1.6 eV). This shift is attributed to the increased coplanarity of the oligomeric inner core, both in the ground (S0) and excited (S1) states, due to the enhanced quinoidal character as supported by bond-length alternation (BLA) analysis. These structural changes promote better π-electron delocalization and facilitate photoinduced charge transfer processes in optoelectronic devices. Notably, we show that Pz- and Tz-containing molecules exhibit NIR electrochromic behavior and present ambivalent character in bulk heterojunction (BHJ) solar cells. Finally, theoretical calculations suggest that these molecules could serve as effective two-photon absorption (2PA) probes, further expanding their potential in optoelectronic applications.

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In situ forming injectable hydrogels hold great potential for the treatment of irregular wounds. However, their practical applications were hindered by long gelation time, poor mechanical performance, and a lack of a natural extracellular matrix structure. Herein, amino-modified electrospun poly(lactic-co-glycolic acid) (APLGA) short fibers with uniform distribution were introduced into gelatin methacrylate/oxidized dextran (GM/ODex) hydrogels. In comparison with the fiber aggregation structure in the PLGA fiber-incorporated hydrogels, the hydrogels with APLGA fibers possessed a uniform porous structure. The highly dispersed APLGA short fibers accelerated the sol–gel phase transition of the hydrogel due to the formation of dynamic Schiff-base bonds between the fibers and hydrogels. Furthermore, in combination with UV-assisted crosslinking, a rapid gelation time of 90 s was achieved for the double-crosslinked hydrogels. The addition of APLGA short fibers as fillers and the formation of the double-crosslinking network enhanced the mechanical performance of the hydrogels. Furthermore, the fiber–hydrogel composites exhibited favorable injectability, excellent biocompatibility, and improved cell infiltration. In vivo assessment indicated that the GM/ODex-APLGA hydrogels successfully filled the full-thickness defects and improved wound healing. This work demonstrates a promising solution for the treatment of irregular wounds.

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Utilization of CoO@Co3O4-x-Ag (x denotes 1, 3, and 5 wt% of Ag) nanocomposites as supercapacitor electrodes is the main aim of this study. A new low-temperature wet chemical approach is proposed to modify the commercial cobalt oxide material with silver nanoparticle (NP) balls of size 1–5 nm. The structure and morphology of the as-prepared nanocomposites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption–desorption measurements. Hydrogels known to be soft but stable structures were used here as perfect carriers for conductive nanoparticles such as carbons. Furthermore, hydrogels with a large amount of water in their network can give more flexibility to the system. Fabrication of an electrochemical cell can be achieved by combining these materials with a layer-by-layer structure. The performance characteristics of the cells were examined by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge discharge (GCD). Cobalt oxide modified with 5 wt% Ag gave the best supercapacitor results, and the cell offers a specific capacitance of ∼38 mF cm−2 in two-electrode configurations.

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The emergence of portable electronics in miniaturized and intelligent devices demands high-performance supercapacitors (SC) and batteries as power sources. For the fabrication of such energy storage devices, conducting polymers (CPs) have significant advantages due to their high theoretical capacitive performance and conductivity. In this work, we developed two CPs including polyaniline and polythiophene through a low-cost chemically synthesized approach and the film-by-spin coating method. The structural and morphological properties of the CPs are analyzed using Fourier-transform infrared spectroscopy (FTIR), contact angle measurement, and scanning electron microscopy (SEM). Based on these CPs, novel pristine polyaniline and polythiophene-based SCs (PASC and PTSC) are developed. The prepared CPs contribute to high electrochemical performances due to their high conductive nature of the electrode and conjugated polymer materials reaction. Hence both electrochemical double-layer formation and pseudocapacitance contributed to the energy-storing performances of the device. Electrochemical impedance spectroscopic analysis (0.1 Hz to 100 kHz) demonstrates faster ionic exchange and high capacitance of the PASC electrode as compared to PTSC in H3PO4 electrolyte. The PASC devices exhibit specific capacitance of 13.22 mF·cm−2 with energy and power densities of 1.175 μW·h·cm−2 and 4.99 μW·cm−2 at a current of 50 μA. Compared to PTSC (specific capacitance 3.30 mF·cm−2) the PASC shows four times higher specific capacitance due to its improved surface, structural and electrical properties. The electrochemical performance reveals the superior SC performance for this type of CP electrode.

Słowa kluczowe:

Conductive polymers, Spin coating, Polyaniline, Polythiophene, Supercapacitor, Electrochemical performances

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The four most popular water models in molecular dynamics were studied in large-scale simulations of Brownian motion of colloidal particles in optical tweezers and then compared with experimental measurements in the same time scale. We present the most direct comparison of col- loidal polystyrene particle diffusion in molecular dynamics simulations and experimental data on the same time scales in the ballistic regime. The four most popular water models, all of which take into account electrostatic interactions, are tested and compared based on yielded results and re- sources required. Three different conditions were simulated: a freely moving particle and one in a potential force field with two different strengths based on 1 pN/nm and 10 pN/nm. In all cases, the diameter of the colloidal particle was 50 nm. The acquired data were compared with experimental measurements performed using optical tweezers with position capture rates as high as 125 MHz. The experiments were performed in pure water on polystyrene particles with a 1 μm diameter in special microchannel cells.

Słowa kluczowe:

Brownian motion,molecular dynamics,optical tweezers,ballistic regime

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Three new ionic polythiophene derivatives, soluble in polar solvents, are synthesized with good yields using simple, low-cost, and straightforward procedures. They are investigated as interfacial cationic conjugated
polyelectrolyte (CPE) layers for halogen-free bulk heterojunction polymeric solar cells, based on a water-soluble electron-donor polymer
(poly[3-(6-diethanolaminohexyl)thiophene]) and a water-soluble electron-acceptor fullerene derivative (malonodiserinolamide fullerene). The simple insertion of the CPE interlayer between the active layer and the aluminum cathode dramatically increases the power conversion efficiency of the final device up to nearly 5%, resulting from a decrease of the electrode work function, improved electron extraction, and optimization of the morphology of the layers. The obtained results demonstrate that the incorporation of CPE layer is a powerful and convenient methodology for the
development of highly efficient and eco-friendly processable polymeric solar cells.

Słowa kluczowe:

conjugated polyelectrolyte,electron transport layers,polythiophene

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Cross-linking of poly(vinyl alcohol) (PVA) creates a three-dimensional network by bonding adjacent polymer chains. The cross-linked structure, upon immersion in water, turns into a hydrogel, which exhibits unique absorption properties due to the presence of hydrophilic groups within the PVA polymer chains and, simultaneously, ceases to be soluble in water. The properties of PVA can be adjusted by chemical modification or blending with other substances, such as polymers, e.g., conductive poly[3-(potassium-5-butanoate)thiophene-2,5-diyl] (P3KBT). In this work, PVA-based conductive semi-interpenetrating polymer networks (semi-IPNs) are successfully fabricated. The systems are obtained as a result of electrospinning of PVA/P3KBT precursor solutions with different polymer concentrations and then cross-linking using “green”, environmentally safe methods. One approach consists of thermal treatment (H), while the second approach combines stabilization with ethanol and heating (E). The comprehensive characterization allows to evaluate the correlation between the cross-linking methods and properties of nanofibrous hydrogels. While both methods are successful, the cross-linking density is higher in the thermally cross-linked samples, resulting in lower conductivity and swelling ratio compared to the E-treated samples. Moreover, the H-cross-linked systems have better mechanical properties─lower stiffness and greater tensile strength. All the tested systems are biocompatible, and interestingly, due to the presence of P3KBT, they show photoresponsivity to solar radiation generated by the simulator. The results indicate that both methods of PVA cross-linking are highly effective and can be applied to a specific system depending on the target, e.g., biomedical or electronic applications.

Słowa kluczowe:

poly(vinyl alcohol),poly[3-(potassium-5-butanoate)thiophene-2.5-diyl],electrospun nanofibers,cross-linking,fibrous hydrogel,semi-IPN

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Over the last few years, traditional drug delivery systems (DDSs) have been transformed into smart DDSs. Recent advancements in biomedical nanotech-nology resulted in introducing stimuli-responsiveness to drug vehicles. Nano-
platforms can enhance drug release efficacy while reducing the side effects of drugs by taking advantage of the responses to specific internal or external stim-uli. In this study, we developed an electrospun nanofibrous photo-responsive DDSs. The photo-responsivity of the platform enables on-demand elevated drug release. Furthermore, it can provide a sustained release profile and pre-vent burst release and high concentrations of drugs. A coaxial electrospinning setup paired with an electrospraying technique is used to fabricate core-shell PVA-PLGA nanofibers decorated with plasmonic nanoparticles. The fabricated
nanofibers have a hydrophilic PVA and Rhodamine-B (RhB) core, while the shell is hydrophobic PLGA decorated with gold nanorods (Au NRs). The presence of plasmonic nanoparticles enables the platform to twice the amount of drug release besides exhibiting a long-term release. Investigations into the photo-responsive release mechanism demonstrate the system's potential as a “smart” drug delivery platform.

Słowa kluczowe:

electrospun core-shell nanofibers,NIR-light activation,on-demand drug release,plasmonic nanoparticles,stimuli-responsive nanomaterials

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In recent times, the use of personal protective equipment, such as face masks or respirators, is becoming more and more critically important because of common pollution; furthermore, face masks have become a necessary element in the global fight against the COVID-19 pandemic. For this reason, the main mission of scientists has become the development of face masks with exceptional properties that will enhance their performance. The versatility of electrospun polymer nanofibers has determined their suitability as a material for constructing “smart” filter media. This paper provides an overview of the research carried out on nanofibrous filters obtained by electrospinning. The progressive development of the next generation of face masks whose unique properties can be activated in response to a specific external stimulus is highlighted. Thanks to additional components incorporated into the fiber structure, filters can, for example, acquire antibacterial or antiviral properties, self-sterilize the structure, and store the energy generated by users. Despite the discovery of several fascinating possibilities, some of them remain unexplored. Stimuli-responsive filters have the potential to become products of large-scale availability and great importance to society as a whole.

Słowa kluczowe:

nanostructured face masks, stimuli-responsive nanomaterials, electrospun nanofibers, active filtration, smart filters, COVID-19, antipathogen

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The use of injectable biomaterials for cell delivery is a rapidly expanding field which may revolutionize the medical treatments by making them less invasive. However, creating desirable cell carriers poses significant challenges to the clinical implementation of cell-based therapeutics. At the same time, no method has been developed to produce injectable microscaffolds (MSs) from electrospun materials. Here the fabrication of injectable electrospun nanofibers is reported on, which retain their fibrous structure to mimic the extracellular matrix. The laser-assisted micro-scaffold fabrication has produced tens of thousands of MSs in a short time. An efficient attachment of cells to the surface and their proliferation is observed, creating cell-populated MSs. The cytocompatibility assays proved their biocompatibility, safety, and potential as cell carriers. Ex vivo results with the use of bone and cartilage tissues proved that NaOH hydrolyzed and chitosan functionalized MSs are compatible with living tissues and readily populated with cells. Injectability studies of MSs showed a high injectability rate, while at the same time, the force needed to eject the load is no higher than 25 N. In the future, the produced MSs may be studied more in-depth as cell carriers in minimally invasive cell therapies and 3D bioprinting applications.

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We report the influence of the partial substitution of Ge with Ti on the properties of NASICON Li1.5Al0.5Ge1.5(PO4)3 (LAGP) nanofibers prepared by electrospinning. Replacing a small amount of Ge (up to 20%) with Ti is advantageous for enhancing both the purity and morphology of LAGP fibers, as observed by X-ray diffraction, electron microscopy and nuclear magnetic resonance spectroscopy. When Ti-substituted LAGP (LAGTP) fibers are used as filler to develop composite polymer electrolytes, the ionic conductivity at 20 °C improves by a factor of 1.5 compared to the plain polymer electrolyte. Additionally, above 40 °C the LAGTP fiber-based composite electrolytes were more conductive than the equivalent LAGP fiber-based one. We believe that these findings can make a substantial contribution to optimizing current methods and developing novel synthesis approaches for NASICON based electrolytes.

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One of the most fascinating areas in the field of smart biopolymers is biomolecule sensing. Accordingly, multifunctional biomimetic, biocompatible, and stimuli-responsive materials based on hydrogels have attracted much interest. Within this framework, the design of nanostructured materials that do not require any external energy source is beneficial for developing a platform for sensing glucose in body fluids. In this article, we report the realization and application of an innovative platform consisting of two outer layers of a nanocomposite plasmonic hydrogel plus one inner layer of electrospun mat fabricated by electrospinning, where the outer layers exploit photoinitiated free radical polymerization, obtaining a compact and stable device. Inspired by the exceptional features of chameleon skin, plasmonic silver nanocubes are embedded into a poly(N-isopropylacrylamide)-based hydrogel network to obtain enhanced thermoresponsive and antibacterial properties. The introduction of an electrospun mat creates a compatible environment for the homogeneous hydrogel coating while imparting excellent mechanical and structural properties to the final system. Chemical, morphological, and optical characterizations were performed to investigate the structure of the layers and the multifunctional platform. The synergetic effect of the nanostructured system’s photothermal responsivity and antibacterial properties was evaluated. The sensing features associated with the optical properties of silver nanocubes revealed that the proposed multifunctional system is a promising candidate for glucose-sensing applications.

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Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, allowing for the fabrication of bulk heterojunction (BHJ) solar cells using environmentally friendly conditions. All polymers were fully characterized by spectroscopic, thermal, electrochemical, X-ray diffraction, scanning electron, and atomic force techniques. BHJ solar cells were obtained from halogen-free solvents (i.e., ethanol and/or anisole) by blending the synthesized ionic push–pull polymers with a serinol-fullerene derivative or an ionic homopolymer acting as electron-acceptor (EA) or electron-donor (ED) counterparts, respectively. The device with the highest optical density and the smoothest surface of the active layer was the best-performing, showing a 4.76% photoconversion efficiency.

Słowa kluczowe:

donor–acceptor systems, bifunctional materials, phosphonium salts, eco-friendly BHJ solar cells, anisole

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The recent burst of research on smart materials is a clear evidence of the growing interest of the scientific community, industry, and society in the field. The exploitation of the great potential of stimuli-responsive materials for sensing, actuation, logic, and control applications is favored and supported by new manufacturing technologies, such as electrospinning, that allows to endow smart materials with micro- and nanostructuration, thus opening up additional and unprecedented prospects. In this wide and lively scenario, this article systematically reviews the current advances in the development of thermoactive electrospun fibers and textiles, sorting them, according to their response to the thermal stimulus. Hence, several platforms including thermoresponsive systems, shape memory polymers, thermo-optically responsive systems, phase change materials, thermoelectric materials, and pyroelectric materials, are described and critically discussed. The difference in active species and outputs of the aforementioned categories is highlighted, evidencing the transversal nature of temperature stimulus. Moreover, the potential of novel thermoactive materials are pointed out, revealing how their development could take to utmost interesting achievements.

Słowa kluczowe:

electrospinning, phase change materials, pyroelectric materials, shape memory polymers, thermoelectric materials, thermo-optically responsive materials, thermoresponsive materials

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Adhesive and stretchable nanofibrous hydrogels have attracted extensive attraction in wound dressings, especially for joint wound treatment. However, adhesive hydrogels tend to display poor stretchable behavior. It is still a significant challenge to integrate excellent adhesiveness and stretchability in a nanofibrous hydrogel. Herein, a highly adhesive, stretchable, and breathable nanofibrous hydrogel was developed via an in situ hybrid cross-linking strategy of electrospun nanofibers comprising dopamine (DA) and gelatin methacryloyl (GelMA). Benefiting from the balance of cohesion and adhesion based on photocross-linking of methacryloyl (MA) groups in GelMA and the chemical/physical reaction between GelMA and DA, the nanofibrous hydrogels exhibited tunable adhesive and mechanical properties through varying MA substitution degrees of GelMA. The optimized GelMA60-DA exhibited 2.0 times larger tensile strength (2.4 MPa) with an elongation of about 200%, 2.3 times greater adhesive strength (9.1 kPa) on porcine skin, and 3.1 times higher water vapor transmission rate (10.9 kg m–2 d–1) compared with gelatin nanofibrous hydrogels. In parallel, the GelMA60-DA nanofibrous hydrogels could facilitate cell growth and accelerate wound healing. This work presented a type of breathable nanofibrous hydrogels with excellent adhesive and stretchable capacities, showing great promise as wound dressings.

Słowa kluczowe:

nanofibrous hydrogels, hybrid cross-linking, adhesivity, stretchability, breathable capability

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The importance of having a fast, accurate, and reusable track for detection has led to an increase investigation in the field of biosensing. Optical biosensing using plasmonic nanoparticles, such as gold and silver, introduces localized surface plasmon resonance (LSPR) sensors. LSPR biosensors are progressive in their sensing precision and detection limit. Also, the possibility to tune the sensing range by varying the size and shape of the particles has made them extremely useful. Hydrogels being hydrophilic 3D networks can be beneficial when used as matrices, because of a more efficient biorecognition. Stimuli-responsive hydrogels can be great candidates, as their response to a stimulus can increase recognition and detection. This article highlights recent advances in combining hydrogels as a matrix and plasmonic nanoparticles as sensing elements. The end capability and diversity of these novel biosensors in different applications in the near future are discussed.

Słowa kluczowe:

Smart materials, Plasmonic hydrogel, Biosensing

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Intrinsically conducting polymers (ICPs) are widely used to fabricate biomaterials; their application in neural tissue engineering, however, is severely limited because of their hydrophobicity and insufficient mechanical properties. For these reasons, soft conductive polymer hydrogels (CPHs) are recently developed, resulting in a water-based system with tissue-like mechanical, biological, and electrical properties. The strategy of incorporating ICPs as a conductive component into CPHs is recently explored by synthesizing the hydrogel around ICP chains, thus forming a semi-interpenetrating polymer network (semi-IPN). In this work, a novel conductive semi-IPN hydrogel is designed and synthesized. The hybrid hydrogel is based on a poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide) hydrogel where polythiophene is introduced as an ICP to provide the system with good electrical properties. The fabrication of the hybrid hydrogel in an aqueous medium is made possible by modifying and synthesizing the monomers of polythiophene to ensure water solubility. The morphological, chemical, thermal, electrical, electrochemical, and mechanical properties of semi-IPNs were fully investigated. Additionally, the biological response of neural progenitor cells and mesenchymal stem cells in contact with the conductive semi-IPN was evaluated in terms of neural differentiation and proliferation. Lastly, the potential of the hydrogel solution as a 3D printing ink was evaluated through the 3D laser printing method. The presented results revealed that the proposed 3D printable conductive semi-IPN system is a good candidate as a scaffold for neural tissue applications.

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Over the last decade, nanotechnology and nanomaterials have attracted enormous interest due to the rising number of their applications in solar cells. A fascinating strategy to increase the efficiency of organic solar cells is the use of tailor-designed buffer layers to improve the charge transport process. High-efficiency bulk heterojunction (BHJ) solar cells have been obtained by introducing hollow core polyaniline (PANI) nanofibers as a buffer layer. An improved power conversion efficiency in polymer solar cells (PSCs) was demonstrated through the incorporation of electrospun hollow core PANI nanofibers positioned between the active layer and the electrode. PANI hollow nanofibers improved buffer layer structural properties, enhanced optical absorption, and induced a more balanced charge transfer process. Solar cell photovoltaic parameters also showed higher open-circuit voltage (+ 40.3%) and higher power conversion efficiency (+ 48.5%) than conventional architecture BHJ solar cells. Furthermore, the photovoltaic cell developed achieved the highest reported efficiency value ever reached for an electrospun fiber-based solar cell (PCE = 6.85%). Our results indicated that PANI hollow core nanostructures may be considered an effective material for high-performance PSCs and potentially applicable to other fields, such as fuel cells and sensors.

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The Coronavirus disease 2019 (COVID‐19) emergency has demonstrated that the utilization of face masks plays a critical role in limiting the outbreaks. Healthcare professionals utilize masks all day long without replacing them very frequently, thus representing a source of cross‐infection for patients and themselves. Nanotechnology is a powerful tool with the capability to produce nanomaterials with unique physicochemical and anti‐pathogen properties. Here, we outline how to realize non‐disposable and highly comfortable respirators with light‐triggered self‐disinfection ability by bridging bioactive nanofiber properties and stimuli‐responsive nanomaterials. The visionary road highlighted in this Concept is based on the possibility to develop a new generation of masks based on multifunctional membranes where the presence of nanoclusters and plasmonic nanoparticles arranged in a hierarchical structure enables the realization of a chemically‐driven and on‐demand anti‐pathogen activities. Multilayer electrospun membranes have the ability to dissipate humidity present within the mask, enhancing the wearability and usability. The photo‐thermal disinfected membrane is the core of these 3D printed and reusable masks with moisture pump capability. Personalized face masks with smart nano‐assisted destruction of pathogens will bring enormous advantages to the entire global community, especially for front‐line personnel, and will open up great opportunities for innovative medical applications.

Słowa kluczowe:

face masks, light-responsive nanomaterials, anti-pathogen, electrospinning, digitally personalized

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Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D–A′–D–A–D–A′–D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl vs. thioalkyl substituted thiophene ring) have been varied to finely tune the chemical-physical properties of the D–A oligomers, to affect the packing arrangement in the solid-state as well as to enhance the photovoltaic performances. The optoelectronic properties of all compounds have been studied by means of optical spectroscopy, electrochemistry, and density functional theory calculations. Electrochemical measurements and Kelvin probe force microscopy (KPFM) predicted a bifunctional behaviour for these oligomers, suggesting the possibility of using them as donor materials when blended with PCBM, and as acceptor materials when coupled with P3HT. Investigation of their photovoltaic properties confirmed this unusual characteristic, and it is shown that the performance can be tuned by the different substitution pattern. Furthermore, thanks to their ambivalent character, binary non-fullerene small-molecule organic solar cells with negligible values of HOMO and LUMO offsets were also fabricated, resulting in PCEs ranging between 2.54–3.96%.

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To date, Additive Manufacturing (AM) has come to the fore as a major disruptive technology embodying two main research lines – developing increasingly sophisticated printing technologies and new processable materials. The latter has fostered a tremendous leap in AM technological advancement, allowing 3D printing to play a central role in dictating the tailorable settings for material design. In particular, the manufacturing of three-dimensional (3D) objects with functional hierarchical porous structure is of the utmost importance for numerous research areas, including tissue engineering, catalysis, aerospace, environmental science, electrochemistry, energy and sound absorption and light engineering materials. Biphasic inks such as emulsions, foams, and solid dispersions represent viable templating systems to realise multiscale porosity. The combination of AM techniques and biphasic inks provide pivotal control over multiple levels of material structure and function, enabling the use of advanced materials with unprecedented 3D architectures as well as physical, chemical, and mechanical properties. The related potential benefits are significant, with functional perspectives for a wide variety of research fields. In this concise review, we provide an updated overview of the employment of biphase inks and show how they are adapted to different AM technologies or vice versa.

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A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.

Słowa kluczowe:

water-soluble polymers, double-cable copolymers, polythiophenes, GRIM polymerization, tributylphosphine, water-soluble fullerenes, OPVs

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The spread of antimicrobial resistance requires the development of novel strategies to combat superbugs. Bacteriolytic enzymes (enzybiotics) that selectively eliminate pathogenic bacteria, including resistant strains and biofilms, are attractive alternatives to antibiotics, also as a component of a new generation of antimicrobial wound dressings. AuresinePlus is a novel, engineered enzybiotic effective against Staphylococcus aureus—one of the most common pathogenic bacteria, found in infected wounds with a very high prevalence of antibiotic resistance. We took advantage of its potent lytic activity, selectivity, and safety to prepare a set of biodegradable PLGA/chitosan fibers generated by electrospinning. Our aim was to produce antimicrobial nonwovens to deliver enzybiotics directly to the infected wound and better control its release and activity. Three different methods of enzyme immobilization were tested: physical adsorption on the previously hydrolyzed surface, and covalent bonding formation using N-hydroxysuccinimide/N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide (NHS/EDC) or glutaraldehyde (GA). The supramolecular structure and functional properties analysis revealed that the selected methods resulted in significant development of nanofibers surface topography resulting in an efficient enzybiotic attachment. Both physically adsorbed and covalently bound enzymes (by NHS/EDC method) exhibited prominent antibacterial activity. Here, we present the extensive comparison between methods for the effective attachment of the enzybiotic to the electrospun nonwovens to generate biomaterials effective against antibiotic-resistant strains. Our intention was to present a comprehensive proof-of-concept study for future antimicrobial wound dressing development.

Słowa kluczowe:

antibacterial wound dressings, enzybiotic, fibers functionalization, electrospun wound dressings, Staphylococcus aureus

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In recent years, the main quest of science has been the pioneering of the groundbreaking biomedical strategies needed for achieving a personalized medicine. Ribonucleic acids (RNAs) are outstanding bioactive macromolecules identified as pivotal actors in regulating a wide range of biochemical pathways. The ability to intimately control the cell fate and tissue activities makes RNA-based drugs the most fascinating family of bioactive agents. However, achieving a widespread application of RNA therapeutics in humans is still a challenging feat, due to both the instability of naked RNA and the presence of biological barriers aimed at hindering the entrance of RNA into cells. Recently, material scientists’ enormous efforts have led to the development of various classes of nanostructured carriers customized to overcome these limitations. This work systematically reviews the current advances in developing the next generation of drugs based on nanotechnology-assisted RNA delivery. The features of the most used RNA molecules are presented, together with the development strategies and properties of nanostructured vehicles. Also provided is an in-depth overview of various therapeutic applications of the presented systems, including coronavirus disease vaccines and the newest trends in the field. Lastly, emerging challenges and future perspectives for nanotechnology-mediated RNA therapies are discussed.

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We report the synthesis of ceramic Li1.5Al0.5Ge1.5(PO4)3 (LAGP) nanofibers by combining sol–gel and electrospinning techniques. A homogeneous and stable precursor solution based on chlorides was achieved by controlling Ge hydrolysis. Subsequent electrospinning and heat treatment resulted in highly porous nanostructured NASICON pellets. After a full chemical-physical characterization, various amounts of LAGP nanofibers were used as a filler to develop polyethylene oxide (PEO)-based composite electrolytes. The addition of 10% LAGP nanofibers has allowed doubling the ionic conductivity of the plain polymer electrolyte, by providing longer ion-conductive paths and reducing PEO crystallinity. These findings are promising towards developing solution-based synthesis approaches featuring Ge precursors. In addition, the achieved LAGP nanofibers proved to be a promising nanofiller candidate to develop composite electrolytes for next-generation solid-state batteries.

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A new regioregular polythiophene derivative, called poly[3-(12-hydroxydodecyl)thiophene] (PT12OH), was synthesized by post-functionalizing its ω-brominated precursor poly[3-(12-bromododecyl)thiophene] (PT12Br) prepared using the Grignard metathesis route. Thanks to the optimal balance between hydrophilic and hydrophobic groups within its structure, PT12OH was highly soluble and easily filmable from common organic solvents allowing for its complete characterization. It also showed enhanced thermal properties, crystallinity, and self-assembling capabilities by the formation of strong inter- and intrachain hydrogen bonds. Bulk heterojunction photovoltaic cells with PT12OH and PC61BM showed a PCE of 4.83% and a remarkable over-time stability, offering good photoconversion efficiency even after 120 h of accelerated aging. Indeed, the PCE decrease was 34% for the hydroxylated polymer and 65% for its brominated precursor. It should also be pointed out that the enhanced thermal stability of PT12OH was achieved without resorting to any complex post-annealing photochemical, thermal, or chemical treatment and was thus directly ascribable to the polymer chemical structure. The simple and effective synthetic procedure, photovoltaic efficiency, and enhanced stability revealed the potential of PT12OH for large-scale organic solar cell applications.

Słowa kluczowe:

bulk heterojunction solar cell, regioregular polythiophene derivatives, post-polymerization functionalization, over-time stability

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Thermoplasmonics deals with the generation and manipulation of nanoscale heating associated with noble metallic nanoparticles. To this end, gold nanoparticles (AuNPs) are unique nanomaterials with the intrinsic capability to generate a nanoscale confined light-triggered thermal effect. This phenomenon is produced under the excitation of a suitable light of a wavelength that matches the localized surface plasmonic resonance frequency of AuNPs. Liquid crystals (LCs) and hydrogels are temperature-sensitive materials that can detect the host AuNPs and their photo-induced temperature variations. In this perspective, new insight into thermoplasmonics, by describing a series of methodologies for monitoring, detecting, and exploiting the photothermal properties of AuNPs, is offered. From conventional infrared thermography to highly sophisticated temperature-sensitive materials such as LCs and hydrogels, a new scenario in thermoplasmonic-based, next generation, photonic components is presented and discussed. Moreover, a new road in thermoplasmonic-driven biomedical applications, by describing compelling and innovative health technologies such as on-demand drug-release and smart face masks with smart nano-assisted destruction of pathogens, is proposed. The latter represents a new weapon in the fight against COVID-19.Thermoplasmonics deals with the generation and manipulation of nanoscale heating associated with noble metallic nanoparticles. To this end, gold nanoparticles (AuNPs) are unique nanomaterials with the intrinsic capability to generate a nanoscale confined light-triggered thermal effect. This phenomenon is produced under the excitation of a suitable light of a wavelength that matches the localized surface plasmonic resonance frequency of AuNPs. Liquid crystals (LCs) and hydrogels are temperature-sensitive materials that can detect the host AuNPs and their photo-induced temperature variations. In this perspective, new insight into thermoplasmonics, by describing a series of methodologies for monitoring, detecting, and exploiting the photothermal properties of AuNPs, is offered. From conventional infrared thermography to highly sophisticated temperature-sensitive materials such as LCs and hydrogels, a new scenario in thermoplasmonic-based, next generation, photonic components is presented and discussed. Moreover, a new road in thermoplasmonic-driven biomedical applications, by describing compelling and innovative health technologies such as on-demand drug-release and smart face masks with smart nano-assisted destruction of pathogens, is proposed. The latter represents a new weapon in the fight against COVID-19.

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Multifunctional nanomaterials with the ability torespond to near-infrared (NIR) light stimulation are vital for thedevelopment of highly efficient biomedical nanoplatforms with apolytherapeutic approach. Inspired by the mesoglea structure ofjellyfish bells, a biomimetic multifunctional nanostructured pillowwith fast photothermal responsiveness for NIR light-controlled on-demand drug delivery is developed. We fabricate a nanoplatformwith several hierarchical levels designed to generate a series ofcontrolled, rapid, and reversible cascade-like structural changesupon NIR light irradiation. The mechanical contraction of thenanostructured platform, resulting from the increase of temper-ature to 42°C due to plasmonic hydrogel−light interaction, causesa rapid expulsion of water from the inner structure, passing through an electrospun membrane anchored onto the hydrogel core. Themutual effects of the rise in temperature and waterflow stimulate the release of molecules from the nanofibers. To expand thepotential applications of the biomimetic platform, the photothermal responsiveness to reach the typical temperature level forperforming photothermal therapy (PTT) is designed. The on-demand drug model penetration into pig tissue demonstrates theefficiency of the nanostructured platform in the rapid and controlled release of molecules, while the high biocompatibility confirmsthe pillow potential for biomedical applications based on the NIR light-driven multitherapy strategy.

Słowa kluczowe:

bioinspired materials, NIR-light responsive nanomaterials, multifunctional platforms, electrospun nanofibers, plasmonic hydrogel, photothermal-based polytherapy, on-demand drug delivery

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This work describes the morphological, optical, and thermo‐optical properties of a temperature‐sensitive hydrogel poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) [P(NIPAm‐co‐NIPMAm]) film containing a specific amount of gold nanorods (GNRs). The light‐induced thermoplasmonic heating of GNRs is used to control the optical scattering of an initially transparent hydrogel film. A hydrated P(NIPAm‐co‐NIPMAm) film is optically clear at room temperature. When heated to temperatures over 37 °C via light irradiation with a resonant source (λ = 810 nm) to the GNRs, a reversible phase transition from a swollen hydrated state to a shrunken dehydrated state occurs. This phenomenon causes a drastic and reversible change in the optical transparency from a clear to an opaque state. A significant red shift (≈30 nm) of the longitudinal band can also be seen due to an increased average refractive index surrounding the GNRs. This change is in agreement with an ad hoc theoretical model which uses a modified Gans theory for ellipsoidal nanoparticles. Morphological analysis of the composite film shows the presence of well‐isolated and randomly dispersed GNRs. Thermo‐optical experiments demonstrate an all‐optically controlled light attenuator (65% contrast ratio) which can be easily integrated in several modern optical applications such as smart windows and light‐responsive optical attenuators.

Słowa kluczowe:

active plasmonics, gold nanorods, hydrogels, optical attenuators, optical transparency, plasmonic nanoparticles, polymers

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The poor intrinsic mechanical properties of chitosan hydrogels have greatly hindered their practical applications. Inspired by nature, we proposed a strategy to enhance the mechanical properties of chitosan hydrogels by construction of a nanofibrous and cellular architecture in the hydrogel without toxic chemical crosslinking. To this end, electrospun nanofibers including cellulose acetate, polyacrylonitrile, and SiO2 nanofibers were introduced into chitosan hydrogels by homogenous dispersion and lyophilization. With the addition of 30% cellulose acetate nanofibers, the cellular structure could be maintained even in water without crosslinking, and integration of 60% of the nanofibers could guarantee the free-standing structure of the chitosan hydrogel with a low solid content of 1%. Moreover, the SiO2 nanofiber-reinforced chitosan (SiO2 NF/CS) three-dimensional (3D) matrices exhibit complete shape recovery from 80% compressive strain and excellent injectability. The cellular architecture and nanofibrous structure in the SiO2 NF/CS matrices are beneficial for human mesenchymal stem cell adhesion and stretching. Furthermore, the SiO2 NF/CS matrices can also act as powerful vehicles for drug delivery. As an example, bone morphogenetic protein 2 could be immobilized on SiO2 NF/CS matrices to induce osteogenic differentiation. Together, the electrospun nanofiber-reinforced 3D chitosan matrices exhibited improved mechanical properties and enhanced biofunctionality, showing great potential in tissue engineering.

Słowa kluczowe:

chitosan hydrogel, electrospun nanofiber, mechanical property, nanofibrous matrix, tissue engineering

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Body tissues and organs have complex functions which undergo intrinsic changes during medical treatments. For the development of ideal drug delivery systems, understanding the biological tissue activities is necessary to be able to design materials capable of changing their properties over time, on the basis of the patient's tissue needs. In this study, a nanofibrous thermal‐responsive drug delivery system is developed. The thermo‐responsivity of the system makes it possible to self‐regulate the release of bioactive molecules, while reducing the drug delivery at early stages, thus avoiding high concentrations of drugs which may be toxic for healthy cells. A co‐axial electrospinning technique is used to fabricate core–shell cross‐linked copolymer poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) (P(NIPAAm‐co‐NIPMAAm)) hydrogel‐based nanofibers. The obtained nanofibers are made of a core of thermo‐responsive hydrogel containing a drug model, while the outer shell is made of poly‐l‐lactide‐co‐caprolactone (PLCL). The custom‐made electrospinning apparatus enables the in situ cross‐linking of P(NIPAAm‐co‐NIPMAAm) hydrogel into a nanoscale confined space, which improves the electrospun nanofiber drug dosing process, by reducing its provision and allowing a self‐regulated release control. The mechanism of the temperature‐induced release control is studied in depth, and it is shown that the system is a promising candidate as a "smart" drug delivery platform.

Słowa kluczowe:

biomimetic nanomaterials, electrospun core–shell nanofibers, hierarchical nanostructures, smart drug delivery, thermo‐responsive hydrogels

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The dynamics of highly flexible micro- and nano-filaments are important to a variety of biological, medical, and industrial problems. The filament configuration variation and cross-stream migration in a microchannel are affected by thermal fluctuations in addition to elastic and viscous forces. Here, hydrogel nano-filaments with small bending Young's moduli are utilized to elucidate the transitional behavior of elastic Brownian filaments in an oscillatory microchannel flow. A numerical model based on chain elastic dumbbells similar to the Rouse-Zimm model accounting for elastic, viscous, and random Brownian forces is proposed and implemented. In addition, a theoretical model to describe the average orientation–deformation tensor evolution for an ensemble of filaments in an oscillatory flow is proposed. The results are compared with the evolution observed in the experiments.

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Side‐chain C60‐fullerene functionalized alkylthiophene copolymers with different regioregularity and fullerene content are successfully synthesized using a simple and straightforward post‐polymerization functionalization procedure based on a Grignard coupling reaction. The products are employed as single materials in photoactive layers of organic photovoltaic solar cells. The use of double‐cable polymers allows an enhanced control on the nanomorphology of the active blend, reducing the phase‐segregation phenomena as well as the macroscale separation between the electron acceptor and donor components. With the insertion of a thin layer of gold nanoparticles between buffer and active layer of the cells, a conversion efficiency of 5.68% is obtained. Moreover, an increased stability over time is achieved when the copolymers are photocrosslinked immediately after the annealing procedure, leading to acceptable efficiencies even after 80 h of accelerated ageing, a key feature for widespread applicability of the prepared devices.

Słowa kluczowe:

conjugated polymers, fullerenes, functionalization of polymers, metathesis

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Graphene-based materials have demonstrated high chemical stability and are very promising for protection against the corrosion of metal surfaces. For this reason, in this work, protective layers composed of graphene oxide, reduced graphene oxide and their mixtures were investigated, respectively, against the corrosion of the surface of lead induced by water drops. The materials were deposited on a Pb surface from their suspensions using a Meyer rod. The surface chemical composition, morphology and structure of the coatings were studied by X-ray photoemission spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and stylus profilometry. Moreover, a specific methodology based on the evolution of the water contact angle with time was used to evaluate the reactivity of the lead surface. The results show that the graphene-based materials can form an efficient barrier layer against the degradation of the Pb surface and that the degradation process induced by water is reduced by more than 70%. Moreover, unexpectedly, the best protective performance was obtained using graphene oxide as the coating.

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Nanofibrous materials find a wide range of applications, such as vascular grafts, tissue-engineered scaffolds, or drug delivery systems. This phenomenon can be attributed to almost arbitrary biomaterial modification opportunities created by a multitude of polymers used to form nanofibers, as well as by surface functionalization methods. Among these applications, the hemostatic activity of nanofibrous materials is gaining more and more interest in biomedical research. It is therefore crucial to find both materials and nanofiber structural properties that affect organism responses. The present review critically analyzes the response of blood elements to natural and synthetic polymers, and their blends and composites. Also assessed in this review is the incorporation of pro-coagulative substances or drugs that can decrease bleeding time. The review also discusses the main animal models that were used to assess hemostatic agent safety and effectiveness.

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blood-biomaterial interactions, coagulation, electrospinning, nanofibers, platelets, hemorrhage

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The current work studies the electrospun poly (vinyl alcohol) (PVA) nanofibers and its nanocomposites including nanohydroxy apatite (nHAp) and nHAp/cellulose nanofibers (CNFs), emphasizing the impact of nanofillers on the toughness of nanofibers. PVA nanofibers were incorporated with 10 wt% of nHAp and then various amounts of CNF were added to subsequent PVA/nHAp fibrous nanocomposites. The morphology of nonwoven mats was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). While neat PVA nanofibers were smooth and uniform in thickness, the nanofiller loading resulted in thinner fibers with less uniformity. Furthermore, the thermal properties of the nonwoven network of fibers were characterized employing thermogravimetric analysis (TGA). Although the maximum loss mass temperature of PVA was partially reduced upon addition of nanofillers, the onset of decomposition was not altered. The mechanical characterizations were performed using static tensile and dynamic mechanical analysis (DMA). Compared to neat PVA mats, the tensile test of nanocomposites mats demonstrated the significant increase in Young's modulus; however, strain at break was dramatically reduced. In addition, the fracture work was assessed from the area under the stress-strain curve, which showed brittleness of fibrous nanocomposites due to the nanofiller incorporation. Field emission SEM (FE-SEM) was employed to scan the fracture surface of stretched fibers. The increase in modulus of electrospun mats was also shown by DMA in frequency mode. In parallel, both tensile test and DMA confirmed the change in fracture of PVA fibers from a tough to brittle mode, due to the nanofiller addition.

Słowa kluczowe:

electrospun nanocomposites, nanofillers, toughness, mechanical properties

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Three regioregular thiophenic copolymers, characterized by a bromine atom or a C60-fullerene group at different molar ratios at the end of a decamethylenic plastifying side chain, have been successfully synthesized using a straightforward postpolymerization functionalization procedure based on a Grignard coupling reaction. Owing to their good solubility in common organic solvents, the products were fully characterized using chromatographic, spectroscopic, thermal, and morphological techniques and used as single materials in the photoactive layers of organic solar cells. The photoconversion efficiencies obtained with copolymers were compared with those of a reference cell prepared using a physical blend of the precursor homopolymer and [6,6]-phenyl-C61-butyric acid methyl ester. The best results were obtained with COP2, the copolymer with a 21% molar content of C60-functionalized side chains. The use of the double-cable polymer made possible an enhanced control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena as well as the macroscale separation between the electron-acceptor and -donor components, yielding a power conversion efficiency higher than that of the reference cell (4.05 vs 3.68%). Moreover, the presence of the halogen group was exploited for the photo-cross-linking of the active layer immediately after the thermal annealing procedure. The cross-linked samples showed an increased stability over time, leading to good efficiencies even after 120 h of accelerated aging: this was a key feature for the widespread practical applicability of the prepared devices.

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Materials for the treatment of cancer have been studied comprehensively over the past few decades. Among the various kinds of biomaterials, polymer-based nanomaterials represent one of the most interesting research directions in nanomedicine because their controlled synthesis and tailored designs make it possible to obtain nanostructures with biomimetic features and outstanding biocompatibility. Understanding the chemical and physical mechanisms behind the cascading stimuli-responsiveness of smart polymers is fundamental for the design of multifunctional nanomaterials to be used as photothermal agents for targeted polytherapy. In this review, we offer an in-depth overview of the recent advances in polymer nanomaterials for photothermal therapy, describing the features of three different types of polymer-based nanomaterials. In each case, we systematically show the relevant benefits, highlighting the strategies for developing light-controlled multifunctional nanoplatforms that are responsive in a cascade manner and addressing the open issues by means of an inclusive state-of-the-art review. Moreover, we face further challenges and provide new perspectives for future strategies for developing novel polymeric nanomaterials for photothermally assisted therapies.

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The present study aims to theoretically model and verify the mechanical behavior of electrospun fibers of poly(vinyl alcohol) (PVA) reinforced by nanohydroxy apatite (nHAp) and cellulose nanofibers (CNF), the three composites designated as PVA/nHAp, PVA/CNF, and PVA/nHAp/CNF. Tensile tests and AFM nanoindentation studies were used to measure tensile modulus of electrospun scaffolds and single fibers respectively. Halpin–Tsai and Ouali models were applied to predict the stiffness of electrospun mats. Theoretical analysis according to the Halpin–Tsai model showed that CNF have no preferred orientation in the electrospun fibers, particularly at higher filler content. Additionally, this model provided a better prediction than Ouali model, especially at lower filler content. Theoretical models based on the geometry of an unit cell in open-cell structure such as honeycomb, tetrakaidecahedron and cube models simulate electrospun scaffolds. Among the structural models for analysis of porous scaffolds, the honeycomb model showed the best prediction, tetrakaidecahedron model—a moderate one, and cube model was the worst. In general, it was proved by both experiment and theory that the porous structure of electrospun mat caused significant modulus reduction of nanocomposites.

Słowa kluczowe:

Nanocomposites, Cellulose nanofibers, Electrospinning, Modulus

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Two water-soluble regioregular poly(3-alkylthiophene)s, incorporating aminic groups at the end of the side chains, have been synthesized using a post-polymerization functionalization procedure on a ω-bromine substituted polyalkylthiophene. The high solubility of the obtained polymers in water allowed for the preparation of “green” bulk heterojunction solar cells which reached a power conversion efficiency of 4.85% when PC61BM was used as electron-acceptor material. Improved optical absorption and photocurrent have been obtained by interposing a layer of Ag nanoparticles between the buffer and the photoactive layer, leading to a final power conversion efficiency of 5.51%.

Słowa kluczowe:

Water-soluble polythiophene, Bulk heterojunction solar cell, Organic photovoltaic

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Over the past few decades, there has been strong interest in the development of new micro- and nanomaterials for biomedical applications. Their use in the form of capsules, particles or filaments suspended in body fluids is associated with conformational changes and hydrodynamic interactions responsible for their transport. The dynamics of fibres or other long objects in Poiseuille flow is one of the fundamental problems in a variety of biomedical contexts, such as mobility of proteins, dynamics of DNA or other biological polymers, cell movement, tissue engineering, and drug delivery. In this review, we discuss several important applications of micro and nanoobjects in this field and try to understand the problems of their transport in flow resulting from material-environment interactions in typical, crowded, and complex biological fluids. Our aim is to elucidate the relationship between the nano- and microscopic structures of elongated polymer particles and their flow properties, thus opening the possibility to design nanoobjects that can be efficiently transported by body fluids for targeted drug release or local tissue regeneration.

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Physical and chemical factors resulting from the sterilization methods may affect the structure and properties of the materials which undergo this procedure. Poly(l-lactide-co-glicolide) (PLGA) is commonly used for medical applications, but, due to its inadequate mechanical properties, it is not recommended for load-bearing applications. One of the methods for improving PLGA mechanical properties is addition of hydroxyapatite nanoparticles (nHAp). The aim of this study was to evaluate the effect of nanoparticles addition on PLGA structure and properties after gamma radiation. According to our results, reduction of the molecular mass caused by gamma radiation was lower for PLGA with nHAp addition. Differential scanning calorimetry (DSC) analysis indicates an increase of crystallinity caused both by nHAp and gamma radiation. The first phenomenon can be explained by heteronucleation, while the second one is most probably related to higher molecular mobility of degrading polymer. Moreover, addition of nanoparticles increases thermal stability and affects the Young's modulus changes after gamma radiation.

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Highly efficient single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes were fabricated by incorporating electrospun one-dimensional (1D) nanostructures obtained from polymer chain stretching. Poly(3-alkylthiophene) chains were chemically tailored in order to reduce the side effects of charge recombination which severely affected SMOC photovoltaic performance. This enabled us to synthesize a donor–acceptor conjugated copolymer with high solubility, molecular weight, regioregularity, and fullerene content. We investigated the correlations among the active layer hierarchical structure given by the inclusion of electrospun nanofibers and the solar cell photovoltaic properties. The results indicated that SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%). The enhanced performance may be attributed to well-packed and properly oriented polymer chains. Overall, our work demonstrates that the active material structure optimization obtained by including electrospun nanofibers plays a pivotal role in the development of efficient SMOCs and suggests an interesting perspective for the improvement of copolymer-based photovoltaic device performance using an alternative pathway.

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The recent progress in bioengineering has created great interest in the dynamics and manipulation of long, deformable macromolecules interacting with fluid flow. We report experimental data on the cross-flow migration, bending, and buckling of extremely deformable hydrogel nanofilaments conveyed by an oscillatory flow into a microchannel. The changes in migration velocity and filament orientation are related to the flow velocity and the filament's initial position, deformation, and length. The observed migration dynamics of hydrogel filaments qualitatively confirms the validity of the previously developed worm-like bead-chain hydrodynamic model. The experimental data collected may help to verify the role of hydrodynamic interactions in molecular simulations of long molecular chains dynamics.

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The aim of this research was to study the effect of charge polarity applied to the spinning nozzle on the structure and properties of polycaprolactone/chitosan (PCL/CHT) blends, in particular the efficiency of further surface modification by chondroitin sulphate (CS). The observed differences in the morphology and properties of fibres formed at different polarities were interpreted in terms of molecular interactions occurring in the system. FTIR results indicate stronger PCL-chitosan interactions at negative polarity, resulting in lower PCL crystallinity and crystal size distribution determined by DSC, as well as lower wettability. The charge polarity influences PCL/CHT fibre morphology and tailors some of their properties, e.g. wettability, mechanical properties and the efficiency of surface modification. Better efficiency of CS attachment was observed at negative polarity using atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) is most probably related to higher chitosan content at the fibres' surface being attracted by the negative external potential.

Słowa kluczowe:

Polycaprolactone/chitosan nanofibres, Charge potential effect in electrospinning, Polycaprolactone-chitosan interactions

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Water-soluble regioregular poly{3-[(6-sodium sulfonate)hexyl]thiophene} (PT6S) and poly{3-[(6-trimethylammoniumbromide)hexyl]thiophene} (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%).

Słowa kluczowe:

Water-soluble polymer, Polythiophene derivative, Bulk heterojunction, Organic photovoltaic, Interfacial layer

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A novel thiophenic tetramer containing a cinnamate group in the side chain with a functionalization degree of 50% is reported. The tetramer was obtained by means of a simple and straightforward procedure involving the functionalization of a p-methoxyphenoxy substituted thiophenic precursor, which led to a soluble product with a good yield. The oligomer was fully characterized from a structural and chemical point of view and employed for the fabrication of small molecule organic solar cells exploiting the bulk heterojunction (BHJ) architecture. The presence of an UV-light sensitive group in the tetramer allowed the photocrosslinking of tetramer/PCBM blends, giving high values of photocurrent and conversion efficiency for the exposed samples. Moreover, the UV-treated devices showed improved stability, even upon heating for three days at 130 °C, thus confirming that photocrosslinking can strongly reduce phase segregation under severe operational conditions.

Słowa kluczowe:

electronic materials, polymers, fullerenes, nanostructures, electrical characterization, semiconductors

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Electrospinning of chitosan blends is a reasonable idea to prepare fibre mats for biomedical applications. Synthetic and natural components provide, for example, appropriate mechanical strength and biocompatibility, respectively. However, solvent characteristics and the polyelectrolyte nature of chitosan influence the spinnability of these blends. In order to compare the effect of solvent on polycaprolactone/chitosan fibres, two types of the most commonly used solvent systems were chosen, namely 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and acetic acid (AA)/formic acid (FA). Results obtained by various experimental methods clearly indicated the effect of the solvent system on the structure and properties of electrospun polycaprolactone/chitosan fibres. Viscosity measurements confirmed different polymer–solvent interactions. Various molecular interactions resulting in different macromolecular conformations of chitosan influenced its spinnability and properties. HFIP enabled fibres to be obtained whose average diameter was less than 250 nm while maintaining the brittle and hydrophilic character of the nonwoven, typical for the chitosan component. Spectroscopy studies revealed the formation of chitosan salts in the case of the AA/FA solvent system. Chitosan salts visibly influenced the structure and properties of the prepared fibre mats. The use of AA/FA caused a reduction of Young's modulus and wettability of the proposed blends. It was confirmed that wettability, mechanical properties and the antibacterial effect of polycaprolactone/chitosan fibres may be tailored by selecting an appropriate solvent system. The MTT cell proliferation assay revealed an increase of cytotoxicity to mouse fibroblasts in the case of 25% w/w of chitosan in electrospun nonwovens.

Słowa kluczowe:

chitosan, electrospinning, PCL/chitosan fibres, solvent system, chitosan salts

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Composite nanofibers made of a polyaniline-based polymer blend and different thiol-capped metal nanoparticles were prepared using ex situ synthesis and electrospinning technique. The effects of the nanoparticle composition and chemical structure on the electrical properties of the nanocomposites were investigated. This study confirmed that Brust's procedure is an effective method for the synthesis of sub-10 nm silver, gold, and silver-gold alloy nanoparticles protected with different types of thiols. Electron microscopy results demonstrated that electrospinning is a valuable technique for the production of composite nanofibers with similar morphology and revealed that nanofillers are well-dispersed into the polymer matrix. X-ray diffraction tests proved the lack of a significant influence of the nanoparticle chemical structure on the polyaniline chain arrangement. However, the introduction of conductive nanofillers in the polymer matrix influences the charge transport noticeably improving electrical conductivity. The enhancement of electrical properties is mediated by the nanoparticle capping layer structure. The metal nanoparticle core composition is a key parameter, which exerted a significant influence on the conductivity of the nanocomposites. These results prove that the proposed method can be used to tune the electrical properties of nanocomposites.

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In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in-depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four-point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction.

Słowa kluczowe:

electrospun composite nanofibers, poly(3-hexylthiophene), graphene oxide, electrical conductivity, mechanical properties

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The role of mechanical properties is essential to understand molecular, biological materials, and nanostructures dynamics and interaction processes. Atomic force microscopy (AFM) is the most commonly used method of direct force evaluation, but due to its technical limitations this single probe technique is unable to detect forces with femtonewton resolution. In this paper we present the development of a combined atomic force microscopy and optical tweezers (AFM/OT) instrument. The focused laser beam, on which optical tweezers are based, provides us with the ability to manipulate small dielectric objects and to use it as a high spatial and temporal resolution displacement and force sensor in the same AFM scanning zone. We demonstrate the possibility to develop a combined instrument with high potential in nanomechanics, molecules manipulation and biological studies. AFM/OT equipment is described and characterized by studying the ability to trap dielectric objects and quantifying the detectable and applicable forces. Finally, optical tweezers calibration methods and instrument applications are given.

Słowa kluczowe:

optical trap, nanomanipulation, nanomechanics, femtonewton forces

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Recent biomedical hydrogels applications require the development of nanostructures with controlled diameter and adjustable mechanical properties. Here we present a technique for the production of flexible nanofilaments to be used as drug carriers or in microfluidics, with deformability and elasticity resembling those of long DNA chains. The fabrication method is based on the core-shell electrospinning technique with core solution polymerisation post electrospinning. Produced from the nanofibers highly deformable hydrogel nanofilaments are characterised by their Brownian motion and bending dynamics. The evaluated mechanical properties are compared with AFM nanoindentation tests.

Correction: Hydrogel Nanofilaments via Core-Shell Electrospinning, Nakielski P., Pawłowska S., Pierini F., Liwińska W., Hejduk P., Zembrzycki K., Zabost E., Kowalewski T.A., PLOS ONE, ISSN: 1932-6203, DOI: 10.1371/journal.pone.0133458, Vol.10, No.7, pp.e0133458-1-2, 2015

Słowa kluczowe:

Gels, Nanomaterials, Atomic force microscopy, Polymerization, Bending, Mass diffusivity, Mechanical properties, Hydrodynamics

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The aim of this study was to examine the role of the nanofillers spatial arrangement in the electrical properties of hybrid organic-inorganic fibers. In this paper, we have presented experimental results for preparation of fibers with a nanometric diameter based on a polyaniline/poly(ethylene oxide) doped blend and geomimetic chrysotile nanotubes. The nanostructured material was prepared using electrospinning techniques. Electrospun fibers made by pristine polymers and by the same blend loaded with carbon nanotubes were used as reference materials to compare the structural, and electrical properties of the novel organic-inorganic material. Generally, electrical properties were improved by the addition of materials that have high conductivity. Electrospun fibers filled with a traditional insulator like chrysotile have shown higher electrical conductivity than the pristine materials. In order to fully understand how structural variations impact upon the electrical conductivity the materials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), differential scanning calorimetry (DSC) and four-point probe method. The results suggest that the occurred electrical conductivity gain could be attributed to parallel orientation of the chrysotile nanotubes and higher crystallinity induced by the one-dimensional nanostructured filler materials. The obtained results bring us one step closer to using intrinsically conducting polymers (ICPs) in the creation of functionalized polymeric nanocomposites for nanotechnology.

Słowa kluczowe:

Nanocomposites, Conductive polymer, Electrospinning, Chrysotile, Carbon nanotubes

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Synthetic mesoporous Fe doped geoinspired nanotubes have been utilized to evaluate the modification of the surface composition, morphology charge distribution and thermal stability as functions of the Fe doping extent and Fe prevalent substitution into the octahedral or tetrahedral sites. FTIR-ATR spectroscopy analysis has allowed to highlight the chrysotile structure modification by the Fe substitution to Mg or Si and to underline clearly the crucial role of the Fe doping in the octahedral sheet in modifying chrysotile structure and morphology. XPS analysis, ζ-potentials and porosity characterization have allowed to define the propriety of the chrysotile surface structure when iron replaces Mg in octahedral or Si in tetrahedral sites. DTA analysis has allowed to relate the effect of Fe doping on the chemical–physical characteristics of both synthetic and mineral chrysotile. We have observed that the simultaneous decrease in dehydroxylation and recrystallization temperature occurs when the Fe increases on surface and this is due to the increased substitution of Fe in octahedron. The results highlight the relevance to estimate the health hazard of the natural asbestos fibres by valuating the role of Fe surface throughout the use of geoinspired chrysotile synthesised under controlled stoichiometry and structure utilizing it as a selected reference standard.

Słowa kluczowe:

Asbestos, Mesoporous synthetic chrysotile, Geoinspired inorganic nanotubes, Fe doped chrysotile, Surface functionalities

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In this article we demonstrate the use of a blend made of two regioregular polythiophenic derivatives, namely poly(3-methylthio)thiophene and poly(3-hexyl)thiophene, to obtain conductive traces by the simple laser exposure of their thin films to a suitable laser source. The polymeric blend was also tested as a photoactive layer for BHJ solar cells, showing an improved surface morphology and a wider absorption spectrum, thus resulting in an enhanced photovoltaic performance. In the standard condition normally used for the cell preparation, we obtained a 3.16% power conversion efficiency. The device showed good reproducibility and stability over time.

Słowa kluczowe:

Electrical conductivity, Laser tracing, Bulk heterojunction polymeric solar cells, Regioregular polyalkylthiophenes, Polymer blends

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This article describes the preparation of thin films of conjugated polymers which can enhance their specific electrical conductivity by several orders of magnitude by changing their state from insulating to conducting materials. The examined polymers, i.e., a polyacetylenic and a polythiophenic derivative, are functionalized with thioalkylic side chains and are soluble in common organic solvents from which they lead to thick homogeneous films. The films can be deposited on different substrates, either rigid or flexible, and can be easily exposed to laser radiation to make them conductive. The process is irreversible, and the final conductivity is stable over time, even in the presence of high temperatures (up to 180°C), moisture, and air. The high stability of treated samples, easy polymer synthesis and quick and inexpensive suitably tailored laser tracing procedure make these materials very promising for applications in organic electronics and in the development of new electronic circuitry.

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Geomimetic chrysotile nanotubes have a high potentiality in nanotechnological applications. These synthetic inorganic nanotubes can be used to prepare quantum wires with interesting electrical and optical properties. In fact, they behave as host systems, exhibiting a constant inner diameter inferior to 7 nm, a low tendency to aggregate and large inter-channel separation, preventing the interaction between individual guest filled nanomaterial acting as an unisosotropic confining structure. The chemical-physical properties of undoped and differently Fe doped geoinspired chrysotile synthetic nanotubes have been reviewed confirming that these characteristic features make synthetic chrysotile nanotubes excellent candidates to prepare innovative inorganic nanowires. Furthermore, the possibility to synthesize undoped geomimetic chrysotile nanotubes with high reproducibility and crystallinity avoids cytotoxicity, making them safe for human health.

Słowa kluczowe:

chrysotile, geomimetic nanostructures, inorganic nanotubes, nanotechnology, nanowires

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Materials containing suspended micro- or nanomaterials are used extensively in multiple fields of research and industry. In order to understand the behavior of nanomaterials suspended in a liquid, the knowledge of particle stability and mobility is fundamental. For this reason, it is necessary to know the nanoscale solid-solid interaction and the hydrodynamic properties of the particles. In the presented research we used a hybrid Atomic Force Microscope coupled with Optical Tweezers system to measure the femtonewton scale interaction forces acting between single particles and the walls of a microchannel at different separation distances and environmental conditions. We show an important improvement in a typical detection system that increases the signal to noise ratio for more accurate position detection at very low separation distances.

Słowa kluczowe:

Optical Tweezers, Atomic Force Microscopy, particle-wall interaction, colloid stability

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The current task of contemporary fluid mechanics evidently moves from modeling large scale turbulence to lower, molecular scale limit, where assumption of a continuous and deterministic description becomes questionable again. Once the scaling length of flow becomes comparable with structure dimensions, transport phenomena are strongly modulated by molecular interactions and its proper interpretation needs involvement of deeper physics. New experimental tools largely help in understanding transport phenomena at nanoscales. In the following review we give few examples of problems appealing for new theoretical and numerical models embracing continuous flow modeling with molecular scale phenomena.

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Developing an efficient wound dressing has gained significant attention in the biomedical field, as infected wounds can cause severe complications that negatively impact human health. Creating an optimal environment for wound healing and tissue remodeling is crucial. Hydrogel dressings have become increasingly popular for skin repair due to their oxygen permeability, ability to absorb wound exudate, and moisture retention properties1. Additionally, electrospun materials offer unique properties such as biodegradability and the ability to control drug release, which makes them potential candidates for treating infected wounds2. Electrospinning is a simple method for producing ultrafine fibers that range from nano- to micrometers in diameter. Fibers can be used as drug delivery systems, allowing for controlled and on-demand drug release with the addition of stimuli-responsive particles. The main aim of this study was to develop a multi-functional 3D-printed hydrogel composite for infected wound healing. Ketoprofen-loaded poly(lactic-co-glycolic acid) (PLGA) mat incorporated with gold nanorods (AuNRs) was structured to the short filaments (SFs) using the aminolysis method (Fig. 1A). SFs were loaded into 3d printing ink composed of gelatine-methacrylate (GelMA) and alginate sodium (AS) (Fig. 1B). Introducing photo-responsive AuNRs in SFs significantly accelerated the ketoprofen release under near-infrared (NIR) light exposure. The ketoprofen release of the activated platform by NIR light, compared to the non-irradiated system, exhibited a significant elevation of the drug release resulting from the response to the stimuli (Fig. 1C). The composite dressing also showed excellent photo-thermal performance and good mechanical properties. The stability of the print before and after NIR irradiation was also investigated. Moreover, 3D-printed hydrogel demonstrated antibacterial activity under the NIR laser due to the photo-thermal activity, leading to E. coli eradication after multiple times of exposure. Evaluated tests and achieved results paved the way toward further composite’s ex vivo and in vivo application in the field of infected wounds.

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In recent years, novel strategies and approaches to develop antimicrobial biomaterials have attracted increasing attention, targeting multi-functional systems to eliminate bacteria from membranes, surfaces, medical devices, infected sites, contact lenses, etc. More specifically, eradicating bacteria (both resident and exogenous) at the wound site is crucial to guarantee fast and effective wound healing without complications, while sterilization of personal protective equipment (e.g., face masks) makes it possible the safe re-use.[1,2] In this frame, photothermal therapy holds great potential since it can kill pathogenic bacteria with minimal invasiveness.[3]

In this study, plasmonic nanoparticles have been combined with biopolymers to provide the system with bactericide functions. More in detail, plasmonic gold nanorods (AuNRs) are encapsulated into electrospun matrices made of poly(lactic-co-glycolic acid) or polyacrylonitrile by loading into the polymeric solution prior to electrospinning or spraying on the already spun material to obtain the final composites (Figure 1A). The photo-thermal properties of the incorporated AuNRs are exploited to activate the near infrared (NIR)-mediated temperature response upon exposure to NIR light. By reaching a temperature > 55°C, the eradication of 99.5% of bacteria is achieved (Figure 1B), while the stability of the composite materials is maintained. Additionally, in vitro biocompatibility tests performed by culturing fibroblast cells onto the proposed systems show suitable biological properties with no toxic or inflammatory reactions. Taking into account the results, the biocompatible photothermal-responsive nanocomposites reveal their potential in photothermal therapy as a wound dressing and face mask coating.

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Hard-to-heal wounds represent a significant public health problem that often carries a considerable risk of health complications with a negative impact on the quality of a patient's life [1]. The lack of effective treatments for skin damage can be attributed in part to the complexity of a physiological process occurring during the healing and microbial invasion from both resident and exogenous bacteria [2,3]. This research aimed to meet these challenges by developing a multifunctional core-shell nanofiber scaffold releasing the drugs and consisted antimicrobial peptides that hinder bacterial colonization while accelerating the healing process. Core-shell electrospun naofiber systems can control the biomolecule release profile providing sustainable drugs for wound healing. Implemented antimicrobial peptides effectively destroy a large spectrum of pathogens by contact with the cell membrane, decreasing the rate of antibiotic resistance in our healthcare system. The combination of the coaxial system with electrospinning allowed to obtain well-defined fibers. In this study, highly hydrophilic polyvinyl alcohol was confined into water-stable electrospun fibers using optimized polymer blends and cross-linking methods. All employed structures showed ideal morphology, construct's stability over time, and appropriate drug release profile as well as high-cell viability and antimicrobial properties. The developed multifunctional platforms represent a robust and valid candidate for fabricating skin dressings, accelerating the healing of patients' wounds while protecting against bacterial infection.

Słowa kluczowe:

electrospinning, PVA, Green crosslinking

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Lysozyme, an enzyme found in various bodily fluids, holds immense importance as a biomolecule with numerous diagnostic implications. In the realm of ophthalmology, lysozyme detection in tears emerges as a precious tool for identifying and addressing dry and inflamed eyes. To enhance the precision and efficiency of lysozyme detection, Smart materials, such as hydrogels and electrospun nanofibers, have been confirmed to be promising candidates for sensing platforms. Plasmonic nanoparticles, on the other hand, offer enhanced optical properties that allow for localized surface plasmon resonance (LSPR), which has been used alongside these substrates. By integrating these smart materials into biosensing platforms, researchers can achieve rapid, reliable, and non-invasive lysozyme detection from tears.
To achieve this goal, a layered platform consisting of a hydrogel layer, electrospun nanofibers, and plasmonic nanoparticles was designed and fabricated. Electrospun mat of poly (L-lactide-co-caprolactone) (PLCL) was used as the support, providing suitable mechanical properties to the platform. Silver nanoplates were immobilized on top of the electrospun nanofibers, where a layer of poly(N-isopropylacrylamide)-based hydrogel was added. With its porous 3D structure and high water content, the hydrogel network allows enhancement in photothermal responsivity. Moreover, due to its fluid nature, the maneuvering of the biomolecules is much easier, making the biosensing procedure more accurate. The structure of each layer, their cross-section, and the whole platform were investigated chemically, morphologically, and optically. The fast photothermal responsitivity of the platform and sensing features were studied, revealing the applicability of the system as a biosensor for detecting lysozyme.

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Due to their importance in various fields of bio-nanotechnology, the synthesis of thermoresponsive smart polymers has been the focus of recent research. Poly(N-isopropylacrylamide) (PNIPAAm) is a well-known thermal-stimulus responsive polymer that has attracted much attention. For PNIPAAm hydrogels to acquire fast thermo-responsive properties, water molecules must have quick access to the entire material. However, isotropic PNIPAAm-based hydrogels have a slow stimulus-responsivity. Hydrophilic cross-linkable nanostructures are gaining interest as a viable alternative to traditional hydrogels to address this issue. System miniaturization via electrospinning exhibits nanostructures with significantly larger porosity and specific surface area. If the constituting hydrophilic polymer of the electrospun fibrous material were cross-linkable, the resulting would display a rapid hydration/dehydration response. As a result, developing a new class of cross-linkable PNIPAAm copolymers is highly desired.

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Gaining knowledge of the solid-solid interactions and hydrodynamic and mechanical properties is crucial for understanding the processes and dynamics of molecular interactions, biological and nano- structures and also to find their future applications. Atomic force microscopy (AFM) is a versatile technique for nanoscale imaging purposes and for quantify analysis of force at the nanonewton scale. Unfortunately, due to technical limitations and restrictions related to the mechanical properties of cantilevers, this technique cannot detect small forces on the femtonewton scale and analyse the stiffness of very soft materials such as biological tissues or hydrogels. AFM is also use to manipulate materials, however, AFM-based manipulation systems are slow and imprecise. To distinguish, Optical Tweezers (OT) are scientific instruments that can trap small particles and manipulate nano- and micro-materials with much higher precision. The AFM / OT hybrid system is a high-resolution imaging instrument with a lower force limit of detection. It is capable of non-invasively manipulating of nanomaterials, single molecules and living cells, measuring forces with femtonewton accuracy, detecting motion with nanometer (10-9 m) precision and to manipulate objects, but also to obtain images directly in the same sample. The combination of AFM with Optical Tweezers will provide significant advances in biophysical research and in the study of the mechanical properties of nanomaterials [1]. In our system we combine Optical Tweezers with commercial AFM to create an instrument capable of working in hybrid mode. It allows simultaneous manipulation of biological systems of greater complexity and the analysis of their properties. Performed by us, experiments showed that AFM/OT system is a unique technique for visualization of the analysed materials, trapping single micro-objects and measure the interactions (in the range of femtonewton) between single particles. The results obtained by AFM/OT confirm that this equipment is a very useful technique also for determination the mechanical properties of very soft materials (e.g. hydrogels) [2].

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Pulsatile drug delivery systems are gaining a lot of interest because of their numerous advantages, especially when compared to conventional pharmaceutical dosage forms [1]. These materials are time- and site-specific drug delivery systems which can minimize deleterious side effects of conventional drug administration systems. Nevertheless, the delivery systems that are of particular interest are the ones with reversible on-off switching capability, because they allow the delivery of therapeutic agents at the proper time after a predetermined lag time. Among the polymers used for biomedical applications, hydrogels are a class of materials of particular significance, because they can provide spatial and temporal control over the release of various types of drugs. Stimuli-responsive hydrogels can release drugs on-demand with a fast release rate through different mechanisms. The effectiveness of this process can be maximized using nanostructured materials with a large surface-area-to-volume ratio such as electrospun nanofibers. Current challenges in the development of hydrogel electrospun fibrous nanomaterials lie in the lack of spinnability of pure hydrogel precursor solutions. Addressing this issue, we firstly designed a new core-shell nanofibrous material in which the poly(N-isopropylacrylamide)-derivative hydrogel is confined within a shell of a spinnable polymer (Figure 1a). Alternatively, we developed a scaffold material in which electrospun nanofibers loaded with different bioactive molecules where surrounded by a stimuli-responsive hydrogel (Figure 1b). Morphological and chemical characterization as well as drug release studies were carried out to confirm the material’s ability to supply different doses of drugs on demand and to study the release mechanism.

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Stimuli-responsive drug delivery systems are gaining a lot of interest due to their numerous advantages, especially when compared to conventional pharmaceutical dosage forms. One of the examples is photo stimulation that together with nanometer size agents, having high absorption in the near-infrared region, generate heat due to the interaction with light. Stimuli-responsive hydrogels with gold nanorods (AuNRs), that are used as photothermal converters, can aid in releasing drugs on-demand with a fast release rate through different mechanisms. Here we report an easy method for preparing AuNRs encapsulated in a poly(N-isopropylacrylamide) (PNIPAm) hydrogel that release water-soluble drugs due to photo stimulation. PNIPAm-AuNRs demonstrated remote, pulsatile drug release and ex vivo action after irradiation using a NIR laser. Morphological and chemical characterization as well as drug release studies were carried out to confirm the material’s ability to supply different doses of drugs on demand and to study the release mechanism. By combining the photothermal property of AuNRs and thermal-responsive effect of PNIPAm, the hydrogel shows fast thermal/photoresponse, high heating rate, high structural integrity and increased drug release due to phase change mechanism.

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drug delivery systems, nanofibers

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Single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes are considered promising devices for organic solar cells (OSCs). The main efforts in this field focus on the chemical tailoring of polymer molecules to reduce the side effects of charge recombination. These advances have made it possible to obtain a power conversion efficiency (PCE) close to conventional bulk heterojunction (BHJ) cells. So far, however, SMOCs still show inadequate efficiencies due to ineffective charge transport. Here we show how SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%) [1]. The enhanced performance may be attributed to well-packed and properly oriented polymer chains. The hierarchical structure is given by the incorporation of electrospun one-dimensional nanostructures obtained from polymer chain stretching. Our results suggest that the active material optimization obtained by the use of electrospun nanofibers plays a key role in the development of efficient SMOCs.

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Atomic force microscopy (AFM) is an evolution of scanning tunnelling microscopy that immediately gained popularity thanks to its ability to analyse nanomaterials. Initially, AFM was developed for nanomaterials imaging purposes, however the development of new features made it the most commonly used tool for studying the biophysical properties of biological samples. On the other hand, atomic force microscopy has limited use for examining sub-piconewton forces. Few techniques have been developed to measure forces below the AFM limit of detection. Among them, optical tweezers (OT) stand out for their high resolution, flexibility, and because they make it possible to accurately manipulate biological samples and carry out biophysics experiments without side effects thanks to their non-invasive properties. The combination of AFM with other techniques in the last decades has significantly extended its capability. The improvement of the AFM force resolution by developing a hybrid double probe instrument based on the combination of AFM and OT has great potential in cell or molecular biology. [1] We outline principles of atomic force microscopy combined with optical tweezers (AFM/OT) developed by our team underlying the techniques applied during the design, building and instrument use stages. We describe the experimental procedure for calibration of the system and we prove the achievement of a higher resolution (force: 10 fN – spatial: 0.1 nm – temporal: 10 ns) than the stand alone AFM. We show the use of the hybrid equipment in a number of different biophysics experiments performed employing both AFM and OT probes. The presented studies include the demonstration of simultaneous high-precision nanomanipulation and imaging, the evaluation of single biomolecule mechanical properties and the single cell membrane activation and probing. Finally, we show the further potential applications of our AFM/OT.

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AFM, Optical Tweezers

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Electrospun nanofibers are increasingly studied thanks to their potential applications in biomedical devices that include drug delivery systems and tissue engineering scaffolds [1]. Numerous synthetic and natural polymers were used to develop nanofibrous materials. Nanostructured materials high porosity, surface-to- volume ratio together with the ease in surface functionalization and drug incorporation, make them perfect candidates for the development of hemostats. Immediate hemorrhage management becomes crucial to preventing death and serious injury in emergency situations. Severe injuries caused by e.g. traffic accidents are the third leading cause of death worldwide [2]. Research on medical incidents of soldiers stationed in Iraq in 2003-2004 showed that the main cause of death was massive hemorrhage that led to death in about 51% of the rescued soldiers [3]. There is no universal dressing and despite the development of new hemostats, they fail in many preclinical studies. Therefore, there is a need to define most important nanofibrous material characteristics that are responsible for rapid and effective bleeding arrest. There is little research on nanostructured hemostats, regarding the impact of nanofibrous surface on blood and its components. Nonetheless, because of the wide use of nanofibres in wound dressings, artificial blood vessels as well as heart valves, there is knowledge helpful in determining material surface chemistry, wettability and other, which can affect blood coagulation. The very first findings appeared in the research where it was found that even polymers having excellent antiplatelet adhesion abilities, triggered increased platelet adhesion and activation when they were in the form of nanofibers. In several other studies, scaffold morphology, was found to have larger impact on platelet adhesion and activation than differences in the chemistry of the polymers used [4]. More specifically, it was found that materials with fiber diameter higher than 1 µm triggered higher platelet adhesion and aggregation than smaller fibers. In other research, nanofiber stiffness was assessed as more dominating than biological moieties and surface roughness of the nanofiber [5]. In spite of all, analyzed literature presents many contradictory results or findings that had low or no impact on blood clotting in research results of other groups. Hence, additional research and novel experimental methods are needed to find nano features that impact hemostat efficiency.

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blood-biomaterial interactions, nanofibers, clotting

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thermal fluctuations, lateral migration, flexible filaments

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Nanofibers have received considerable attention in the past years, mainly due to their vast application in medicine [1]. One of the fastest growing areas of application are wound dressings and hemostats. Among the major causes of death from trauma, massive bleeding is responsible for 30 – 40% of mortality. In the hospital, massive bleeding are the second most common cause of death (22%) just after cardiac factors (33%) [2]. Despite a large number of experiments done in the topic of blood-biomaterial interactions, coagulation mechanisms are still not fully understood. Therefore, the main objective of our work is the analysis of protein adsorption, platelet adhesion and aggregation, and blood plasma coagulation in the contact with polymer nanofibers. Various synthetic polymers, their blends with natural polymers of confirmed hemostatic effect e.g. collagen and gelatine, and additionally nanofibers made of chitosan are investigated for their potential to stop bleeding. In the final, controlled release of drugs affecting coagulation cascade will be an important step providing accelerated blood clot formation.

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Mobility of hydrogel nanofilaments suspended in liquid is investigated to gain basic knowledge on hydrodynamic interactions biased by Brownian fluctuations. Typical for long macromolecules effects like spontaneous conformational changes and cross-flow migration are observed and evaluated. The collected experimental data can be used to validate assumptions present in numerical models describing intercellular transport of long biomolecules.

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persistence length, macromolecules, electrospinning, DNA, Brownian motion

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Atomic force microscopy (AFM) is the most commonly used method of direct force evaluation, but due to its technical limitations this single probe technique is unable to detect forces with femtonewton resolution. We present the development of a combined atomic force microscopy and optical tweezers (AFM/OT) instrument. The optical tweezers system provides us the ability to manipulate small dielectric objects and to use it as a high spatial and temporal resolution displacement and force sensor in the same AFM scanning zone. We demonstrate the possibility to develop a combined instrument with high potential in nanomechanics, molecules manipulation and biologic al studies. The presented study is aimed to quantify the interaction forces between two single polystyrene particles in the femtonewton scale by using the developed AFM/OT equipment.

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optical trap, nanomanipulation, femtonewtons

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Hydrogel Nanofilaments, Bending Dynamics, Poiseuille Flow, Electrospinning

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Atomic force microscopy/optical tweezers, Nanomanipulation, Single particles analysis, Interaction force measurement, DLVO theory

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electrospinning, fibres, surface, chitosan

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nanofilaments, hydrogel, long molecules flexibility

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We propose a microscale experimental model in form of highly deformable nanofilaments, which permits for precise optical measurements and to evaluate hydrodynamic interactions (mobility). The conducted research includes determination of the mechanical properties of elastic hydrogel nanofilaments obtained by electrospinning that can serve as experimental benchmark to validate theoretical and numerical models describing dynamics of long biological molecules (e.g. proteins, DNA). Nanofilaments mechanical properties are determined by studying their dynamic bending. in shear flow and deformations due to the thermal fluctuations (Brownian motion). These results are compared with AFM nanoindentation measurements. Data obtained from this research project will be a base to crea te biocompatible nanoobjects that can become tools for the regeneration of tissue (e.g. neural tissue).

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Biocompatible nanoobjects, highly deformable nanofilaments, regeneration of tissue

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Nanofilaments, hydrogel filaments, nanofibres, long nanoobjects deformability

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Controlled drug delivery systems are used to improve the conventional administration of drugs. One of the main challenges is to synthesize materials able to find a defined target and to release drugs in a controlled manner [1]. Several research tasks have been focused on developing ideal drug delivery systems made by hydrogel due to their unique properties [2]. The present study is based on the idea that soft and flexible nanomaterials can easily travel in crowed environments of body fluids and biological tissues. Modification of their mechanical properties obtained by changing of the cross-linker amount may give us the possibility to tune the material rigidity according to desired application. Here, we describe a novel method based on coaxial electrospinning for obtaining highly flexible hydrogel nanofilaments able to transport and release dedicated molecules. Two different types of hydrogels (poly(N,Nisopropyl acrylamide) and polyacrylamide) with three polymer/cross-linker ratios were produced and deeply studied. The nanofilaments morphology was characterized and the release of bovine serum albumin as a function of time was quantified. Mechanical properties of highly deformable hydrogel nanofilaments were evaluated by bending dynamics and Brownian motion observation techniques. The calculated mechanical properties were compared with data obtained by nanoindention. The results highlight the crucial role of morphology and stiffness on mobility of nanofilaments colloid systems. The information gained are fundamental to design nanoobjects with well-defined chemical and physical behaviour.

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Nanofilaments, electrospinning, core-shell method, hydrogel

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In this talk we would like to tackle general question of contemporary fluid dynamics, how far its assumption of a continuous, smooth medium remains useful when size and time scales start to approach molecular ones. The question is not trivial and seems to depend on several additional factors usually minored. For example, when full Navier-Stokes equations are replaced by their linear approximation we are loosing basic characteristics of convective motion, and still we use such approach. Once our fluid becomes granular matter with its own internal properties, proper interpretation of flow interactions with other molecular structures probably needs deeper physics. But still we try to convert such problem to the classical macro/micro scale description. Hence a general question arises, how small does a fluid have to be before it is not a fluid anymore?

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microfluidics, nanofluids, Brownian motion, nanofilaments

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nanomanipulation, optical trap, optical tweezers

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electrospinning, flexible nanorods, Brownian motion

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Nanoparticles, polystyrene beads, surface properties, atomic force microscopy, hydrodynamic properties

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